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Raman SPECTROSCOPY
Submitted by-
Urvashi Arya
14-ICB-403
BSc (Hons) Industrial Chemistry
Under Guidance of-
Prof. Anees Ahmad
Introduction to
Raman
spectroscopy
What is spectroscopy?
Spectroscopy is the study of the interaction
between matter and electromagnetic
radiation.
Sir Chandrasekhara Venkata Raman
 November 7, 1888 – November 21, 1970
 Carried out ground-breaking work in the field of light
scattering, which earned him the 1930 Nobel prize for
Physics
• Discovered the “Raman effect”.
• In 1954, India honoured him with its highest
civilian award, the Bharat Ratna.
 Also independent observations by
Grigory Landsberg and Leonid Mandelstam.
• Raman Spectroscopy is a non-destructive chemical analysis technique
which is used to analyze vibrational, rotational, and other low-
frequency modes in a system, providing information about chemical
structure, crystallinity and molecular interactions.
• When a monochromatic radiation of definite frequency (ʋ ) is passed
through a substance, the light is scattered at right angles to the incident
radiation containing lines of-
i. Incident frequencies
ii. Certain discrete frequencies above or below that of incident
radiation..
• The transmitted lines with same frequency as that of incident radiation
is called Rayleigh scatter.
• However a small amount of light (typically 0.0000001) scattered at
different frequency (or wavelength) is called Raman Scatter.
Electromagnetic Spectrum
Theory of Raman spectra.
When a monochromatic beam is passed through a scatterer (liquid or gas), small
fraction of light is scattered due to collision between molecules of substance and
photons of light. Two cases may arise depending upon whether a collision between
a photon and molecules in it’s ground state is elastic or inelastic in nature.
Case 1- if the collision is elastic – this lead to the appearance of unmodified lines
(or unmodified frequency of light) in the scattered beam and this explain Rayleigh
scattering.
Case 2 - if the collision is inelastic – there will be exchange or transfer of energy
between the scattering molecules and the incident photon leading to the Raman
scattering with the two cases.-
1. the molecule absorbs energy from the incident photon and reaches a higher
rotational vibrational state after excitation and emission of photon. Thus the
energy of emitted photon becomes less, hence frequency of scattering lines is
less than that of incident light. This gives stroke's line of Raman spectra.
2. the molecule imparts some of its intrinsic energy to incident photon ,the
emitted photon has higher energy which corresponds to anti stokes line of
raman spectra where frequency of scattering lines is more than that of incident
light. 7
Energy Scheme for Photon Scattering
Rayleigh
Scattering
(elastic)
Stokes
Scattering
Anti-Stokes
Scattering
h 0
h 0
h 0 h
h
0
m
h 0+h
m
E0+h
E0
m
Raman
(inelastic)
The Raman effect comprises a very small fraction,
about 1 in 107 of the incidentphotons.
Virtual
State
IR
Absorption
Energy
Stokes lines Anti Stokes lines
• The frequency of scattered lines is
more than that of incident light.
• Caused by molecules at higher
energy level which are less
populated.
• These are less intense with low
intensity of absorption.
• At high temperature, molecules
are raised to higher energy state,
thus these gradually increases and
become prominent.
• The frequency of scattered lines
is less than that of incident light
• Caused by molecule at lower
energy level which is more
populated.
• These are more intense with high
intensity of absorption.
• At low temperature, these takes
place more frequently.
Stokes Vs Anti Stoke’s lines
The difference between the frequency of the incident light
and that of scattered light is constant and it depends only
on the nature of substance. It is completely independent of
the frequency of incident light.
If ʋ o is the frequency of incident light and ʋ r is the
frequency of scattered light, then
θʋ = [ ʋ o - ʋ r }
This difference is called the Raman shift.
The various observations made by Raman are called Raman
effect and the spectrum obtained is called Raman spectrum.
RAMAN EFFECT
INSTRUMENTATION
11
Mutual Exclusion Principle
Z
Symmetric molecules Based on polarisability
O = C = O O = C = O
Raman active
IR inactive
Raman inactive
IR active
According to the principle, ‘”All vibrations of a
molecule, with a centre of symmetry, which are
Raman active are infra-red inactive and vice versa”.
+ - +
O = C = O
Raman inactive
IR active
Differences between IR and Raman
methodsS.NO
Raman spectra IR spectra
01 It is due to the scattering of light
by the vibrating molecules.
It is the result of absorption of
light by vibrating molecules.
02 The vibration in Raman is active if
it causes a change in polarisability.
Vibration is IR active if there is
change in dipole moment.
03 Gives an indication of covalent
character in the molecule.
Gives an indication of ionic
character in the molecule.
04 Water can be used as a solvent. Water cannot be used due to it
is opaque to IR.
05 Can be obtained for a compound in
all three states.
IR spectra is quite diffused in
liquid and solid state.
Applications of Raman
spectroscopy
• Raman spectroscopy is commonly used in chemistry, since
vibrational information is specific to the chemical bonds and
symmetry of molecules.Therefore, it provides a fingerprint by
which the molecule can be identified.
• Raman spectroscopy is helps in studying the structure of
molecule and also the structural changes which occur due to
association, dissociation and solvation, study the kinetics of fast
reactions.
SOMEOFTHE IMPORTANTAPPLICATIONS ARE-
 Elucidation of molecular structure
 Nature of chemical bond
 Quantitative analysis of mixture
 Mechanism of tautomerism
Applications of Raman
spectroscopyCarbon Materials
Purity of CNTs
Specifying sp2 and sp3 structure in
carbon materials
Geology and Mineralogy
Gemstone and mineral identification
Fluid inclusions
Mineral and phase distribution in rock
sections
Pharmaceuticals
Compound distribution in tablets
Polymorphic forms
Contaminant identification
Life Sciences
Bio-compatibility
DNA/RNA analysis
Drug/cell interactions
Disease diagnosis
Thank you..

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Raman spectroscopy

  • 1. Raman SPECTROSCOPY Submitted by- Urvashi Arya 14-ICB-403 BSc (Hons) Industrial Chemistry Under Guidance of- Prof. Anees Ahmad
  • 3. What is spectroscopy? Spectroscopy is the study of the interaction between matter and electromagnetic radiation.
  • 4. Sir Chandrasekhara Venkata Raman  November 7, 1888 – November 21, 1970  Carried out ground-breaking work in the field of light scattering, which earned him the 1930 Nobel prize for Physics • Discovered the “Raman effect”. • In 1954, India honoured him with its highest civilian award, the Bharat Ratna.  Also independent observations by Grigory Landsberg and Leonid Mandelstam.
  • 5. • Raman Spectroscopy is a non-destructive chemical analysis technique which is used to analyze vibrational, rotational, and other low- frequency modes in a system, providing information about chemical structure, crystallinity and molecular interactions. • When a monochromatic radiation of definite frequency (ʋ ) is passed through a substance, the light is scattered at right angles to the incident radiation containing lines of- i. Incident frequencies ii. Certain discrete frequencies above or below that of incident radiation.. • The transmitted lines with same frequency as that of incident radiation is called Rayleigh scatter. • However a small amount of light (typically 0.0000001) scattered at different frequency (or wavelength) is called Raman Scatter.
  • 7. Theory of Raman spectra. When a monochromatic beam is passed through a scatterer (liquid or gas), small fraction of light is scattered due to collision between molecules of substance and photons of light. Two cases may arise depending upon whether a collision between a photon and molecules in it’s ground state is elastic or inelastic in nature. Case 1- if the collision is elastic – this lead to the appearance of unmodified lines (or unmodified frequency of light) in the scattered beam and this explain Rayleigh scattering. Case 2 - if the collision is inelastic – there will be exchange or transfer of energy between the scattering molecules and the incident photon leading to the Raman scattering with the two cases.- 1. the molecule absorbs energy from the incident photon and reaches a higher rotational vibrational state after excitation and emission of photon. Thus the energy of emitted photon becomes less, hence frequency of scattering lines is less than that of incident light. This gives stroke's line of Raman spectra. 2. the molecule imparts some of its intrinsic energy to incident photon ,the emitted photon has higher energy which corresponds to anti stokes line of raman spectra where frequency of scattering lines is more than that of incident light. 7
  • 8. Energy Scheme for Photon Scattering Rayleigh Scattering (elastic) Stokes Scattering Anti-Stokes Scattering h 0 h 0 h 0 h h 0 m h 0+h m E0+h E0 m Raman (inelastic) The Raman effect comprises a very small fraction, about 1 in 107 of the incidentphotons. Virtual State IR Absorption Energy
  • 9. Stokes lines Anti Stokes lines • The frequency of scattered lines is more than that of incident light. • Caused by molecules at higher energy level which are less populated. • These are less intense with low intensity of absorption. • At high temperature, molecules are raised to higher energy state, thus these gradually increases and become prominent. • The frequency of scattered lines is less than that of incident light • Caused by molecule at lower energy level which is more populated. • These are more intense with high intensity of absorption. • At low temperature, these takes place more frequently. Stokes Vs Anti Stoke’s lines
  • 10. The difference between the frequency of the incident light and that of scattered light is constant and it depends only on the nature of substance. It is completely independent of the frequency of incident light. If ʋ o is the frequency of incident light and ʋ r is the frequency of scattered light, then θʋ = [ ʋ o - ʋ r } This difference is called the Raman shift. The various observations made by Raman are called Raman effect and the spectrum obtained is called Raman spectrum. RAMAN EFFECT
  • 12. Mutual Exclusion Principle Z Symmetric molecules Based on polarisability O = C = O O = C = O Raman active IR inactive Raman inactive IR active According to the principle, ‘”All vibrations of a molecule, with a centre of symmetry, which are Raman active are infra-red inactive and vice versa”. + - + O = C = O Raman inactive IR active
  • 13. Differences between IR and Raman methodsS.NO Raman spectra IR spectra 01 It is due to the scattering of light by the vibrating molecules. It is the result of absorption of light by vibrating molecules. 02 The vibration in Raman is active if it causes a change in polarisability. Vibration is IR active if there is change in dipole moment. 03 Gives an indication of covalent character in the molecule. Gives an indication of ionic character in the molecule. 04 Water can be used as a solvent. Water cannot be used due to it is opaque to IR. 05 Can be obtained for a compound in all three states. IR spectra is quite diffused in liquid and solid state.
  • 14. Applications of Raman spectroscopy • Raman spectroscopy is commonly used in chemistry, since vibrational information is specific to the chemical bonds and symmetry of molecules.Therefore, it provides a fingerprint by which the molecule can be identified. • Raman spectroscopy is helps in studying the structure of molecule and also the structural changes which occur due to association, dissociation and solvation, study the kinetics of fast reactions. SOMEOFTHE IMPORTANTAPPLICATIONS ARE-  Elucidation of molecular structure  Nature of chemical bond  Quantitative analysis of mixture  Mechanism of tautomerism
  • 15. Applications of Raman spectroscopyCarbon Materials Purity of CNTs Specifying sp2 and sp3 structure in carbon materials Geology and Mineralogy Gemstone and mineral identification Fluid inclusions Mineral and phase distribution in rock sections Pharmaceuticals Compound distribution in tablets Polymorphic forms Contaminant identification Life Sciences Bio-compatibility DNA/RNA analysis Drug/cell interactions Disease diagnosis